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The burning of incense for home use is a widespread practice that has been shown to have significant negative impacts on human health and air quality. However, there is a lack of understanding regarding its emission profiles and associated health risks. To address this knowledge gap, we utilized a state-of-the-art thermal desorption comprehensive two-dimensional gas chromatography-mass spectrometer (TD-GC×GC-MS) to (semi-)quantify the emission factors (EFs) of 317 volatile compounds and thoroughly investigate the organic profiles of incense burning smoke across a full-volatility range. Results showed that toluene (70.8 ± 35.7 μg g-1) is the most abundant compound in incensing-burning smoke, followed by benzene, furfural, and phenol. Phenol, toluene, furfural, 2-furanmethanol, benzene, and benzyl alcohol are the main contributors to ozone and secondary organic aerosol (SOA) estimation. Intermediate volatility organic compounds (IVOCs) accounted for 19.2 % of the total EFs, but 40.0 % of the estimated SOA. Additionally, a novel pixel-based method, combined with aroma analysis, revealed that furfural can act as a key tracer of incense burning, and is responsible for the distinctive flavor of incense smoke. High bioaccumulation potential (BAP) assessment using pixel-based partition coefficient estimation revealed that acenaphthylene, dibenzofuran, and phthalate esters (PAEs) are chemicals of high-risk concern and warrant further control. Our results highlight the critical importance of investigating home-use incense burning and provide new insights into the health impacts of incense burning smoke by novel approaches.

Complying with stricter emissions standards, a new generation of heavy-duty trucks (HDTs) has gradually increased its market share and now accounts for a large percentage of on-road mileage. The potential to improve air quality depends on an actual reduction in both emissions and subsequent formation of secondary pollutants. In this study, the emissions in real-world traffic from Euro VI-compliant HDTs were compared to those from older classes, represented by Euro V, using high-resolution time-of-flight chemical ionization mass spectrometry. Gas-phase primary emissions of several hundred species were observed for 70 HDTs. Furthermore, the particle phase and secondary pollutant formation (gas and particle phase) were evaluated for a number of HDTs. The reduction in primary emission factors (EFs) was evident (∼90%) and in line with a reduction of 28–97% for the typical regulated pollutants. Secondary production of most gas- and particle-phase compounds, for example, nitric acid, organic acids, and carbonyls, after photochemical aging in an oxidation flow reactor exceeded the primary emissions (EFAged/EFFresh ratio ≥2). Byproducts from urea-selective catalytic reduction systems had both primary and secondary sources. A non-negative matrix factorization analysis highlighted the issue of vehicle maintenance as a remaining concern. However, the adoption of Euro VI has a significant positive effect on emissions in real-world traffic and should be considered in, for example, urban air quality assessments., When more stringent Euro VI emission standards replaced Euro V standards, the emissions and secondary formation of both regulated and non-regulated air pollutants reduced significantly.

Atmospheric particles can be viscous. The limitation in diffusion impedes the mass transfer of oxidants from the gas phase to the particle phase and hinders multiphase oxidation processes. On the other hand, nitrate photolysis has been found to be effective in producing oxidants such as OH radicals within the particles. Whether nitrate photolysis can effectively proceed in viscous particles and how it may affect the physicochemical properties of the particle have not been much explored. In this study, we investigated particulate nitrate photolysis in mixed sucrose-nitrate-sulfate particles as surrogates of atmospheric viscous particles containing organic and inorganic components as a function of relative humidity (RH) and the molar fraction of sucrose to the total solute (FSU) with an in situ micro-Raman system. Sucrose suppressed nitrate crystallization, and high photolysis rate constants (∼10-5 s-1) were found, irrespective of the RH. For FSU = 0.5 and 0.33 particles under irradiation at 30% RH, we observed morphological changes from droplets to the formation of inclusions and then likely "hollow" semisolid particles, which did not show Raman signal at central locations. Together with the phase states of inorganics indicated by the full width at half-maxima (FWHM), images with bulged surfaces, and size increase of the particles in optical microscopic imaging, we inferred that the hindered diffusion of gaseous products (i.e., NOx, NOy) from nitrate photolysis is a likely reason for the morphological changes. Atmospheric implications of these results are also presented.

Particulate nitrate photolysis can produce oxidants (i.e., OH, NO2, and NO2-/HNO2) in aqueous droplets and may play a potential role in increased atmospheric oxidative capacity. Our earlier works have reported on the SO2 oxidation promoted by nitrate photolysis to produce sulfate. Here, we used glyoxal as a model precursor to examine the role of particulate nitrate photolysis in the formation of secondary organic aerosol (SOA) from particle-phase oxidation of glyoxal by OH radicals. Particles containing sodium nitrate and glyoxal were irradiated at 300 nm. Interestingly, typical oxidation products of oxalic acid, glyoxylic acid, and higher-molecular-weight products reported in the literature were not found in the photooxidation process of glyoxal during nitrate photolysis in the particle phase. Instead, formic acid/formate production was found as the main oxidation product. At glyoxal concentration higher than 3 M, we found that the formic acid/formate production rate increases significantly with increasing glyoxal concentration. Such results suggest that oxidation of glyoxal at high concentrations by OH radicals produced from nitrate photolysis in aqueous particles may not contribute significantly to SOA formation since formic acid is a volatile species. Furthermore, recent predictions of formic acid/formate concentration from the most advanced chemical models are lower than ambient observations at both the ground level and high altitude. The present study reveals a new insight into the production of formic acid/formate as well as a sink of glyoxal in the atmosphere, which may partially narrow the gap between model predictions and field measurements in both species.

ECIS 2022. 36th European Colloid & Interface Society Conference, 4 -9 September 2022 Chania, Crete, Greece, E.G.N. acknowledges financial support from the Agencia Estatal de Investigación Grant Number PID2020-115722GB-C21.

Photolysis of iron chlorides is a well-known photolytic source of Cl• in environmental waters. However, the role of particulate chlorine radicals (Cl• and Cl2•–) in their multiphase oxidative poten...

The relative humidity (RH) history that manifests the cycling of dehydration (water evaporation) and hydration (water uptake) may affect particle-phase reactions, products from which have strong influences on the physical properties and thus climatic effects of atmospheric particles. Using single-trapped particles, we show herein hygroscopic growths of mixed particles with reactive species undergoing three types of RH cycles, simulating different degrees of particle-phase reactions in the atmosphere. The reactive species are the widely known α-dicarbonyl glyoxal (GLY), and five reduced nitrogenous species, ammonium sulfate (AS), glycine (GC), l-alanine (AL), dimethylamine (DMA), and diethylamine (DEA). The results showed that the mixed particles after reactions generally had altered efflorescence relative humidity (ERH) and deliquescence relative humidity (DRH) values and reduced hygroscopic growths at moderately high RH (80%) conditions. For example, with an additional slow drying step, the mean mass growth factors at 90% RH during dehydration dropped from 2.56 to 2.02 for GC/GLY mixed particles and from 2.45 to 1.23 for AL/GLY mixed particles. The reduced hygroscopicity with more RH cycling will thus lead to less efficient light scattering of the mixed particles, thereby resulting in less cooling and exacerbating direct heating due to light absorption by the products formed.

Aperiodic 2022. 10th International Conference on Aperiodic Crystals, June 20-24, 2022, in Akira Suzuki Hall of Sapporo campus at Hokkaido University, Japan .-- Invited conference

XXIII Congreso de Física Estadística, FisEs’22, Zaragoza, España, 12 – 14 de mayo de 2022

Gaseous nitrous acid (HONO) has the potential to greatly contribute to the atmospheric oxidation capacity. Increased attention has been paid to in-particle nitrite or nitrous acid, N(III), as one of the HONO sources. However, sources and formation mechanisms of N(III) remain uncertain. Here, we study a much less examined reaction of Fe(II) and nitrate as a source of N(III). The N(III) production was indirectly probed by its multiphase reaction with SO2 for sulfate production. Particles containing nitrate and Fe(III) were irradiated for generating Fe(II). Sulfate production was enhanced by the presence of UV and organic compounds likely because of the enhanced redox cycle between Fe(II) and Fe(III). Sulfate production rate increases with the concentration of iron-organic complexes in nitrate particles. Similarly, higher concentrations of iron-organic complexes yield higher nitrate decay rates. The estimated production rates of N(III) under simulated conditions in our study vary from 0.1 to 3.0 μg m-3 of air h-1. These values are comparable to HONO production rates of 0.2-1.6 ppbv h-1, which fall in the values reported in laboratory and field studies. The present study highlights a synergistic effect of the coexistence of iron-organic complexes and nitrate under irradiation as a source of N(III).

A prominent source of hydroxyl radicals (•OH), nitrous acid (HONO) plays a key role in tropospheric chemistry. Apart from direct emission, HONO (or its conjugate base nitrite, NO2-) can be formed secondarily in the atmosphere. Yet, how secondary HONO forms requires elucidation, especially for heterogeneous processes involving numerous organic compounds in atmospheric aerosols. We investigated nitrite production from aqueous photolysis of nitrate for a range of conditions (pH, organic compound, nitrate concentration, and cation). Upon adding small oxygenates such as ethanol, n-butanol, or formate as •OH scavengers, the average intrinsic quantum yield of nitrite [Φ(NO2-)] was 0.75 ± 0.15%. With near-UV-light-absorbing vanillic acid (VA), however, the effective Φ(NO2-) was strongly pH-dependent, reaching 8.0 ± 2.1% at a pH of 8 and 1.5 ± 0.39% at a more atmospherically relevant pH of 5. Our results suggest that brown carbon (BrC) may greatly enhance the nitrite production from the aqueous nitrate photolysis through photosensitizing reactions, where the triplet excited state of BrC may generate solvated electrons, which reduce nitrate to NO2 for further conversion to nitrite. This photosensitization process by BrC chromophores during nitrate photolysis under mildly acidic conditions may partly explain the missing HONO in urban environments.

The domestic emission control area (DECA) policy has been implemented in China since 2017. However, its impact on ship emissions and in turn urban air quality is still unclear. In this study, real-time single particle measurements were carried out at a site in urban Guangzhou, about 1 km downwind of Huangpu Port, the largest maritime transport hub in southern China, in the summer of 2020 using a single particle aerosol mass spectrometer (SPAMS). During the campaign, the hourly averaged number fraction of ship emitted particles, using vanadium as a chemical indicator, varied from 0 to 14% with an average of 2 ± 1%. Ship emitted single particles contain organic carbon (OC), elemental carbon (EC), metals, sulfate and nitrate. More than 95% of ship emitted particles were sulfate-containing particles and the relative peak areas (RPAs) of sulfate and vanadium in the hourly average mass spectra of ship emitted particles were highly correlated (R

Heterogeneous oxidation of SO2 is an effective production pathway of sulfate in the atmosphere. We recently reported a novel pathway for the heterogeneous oxidation of SO2 by in-particle oxidants (...

The chemical speciation of nanoparticles is technically challenging because of the minute mass of the particles. There is a constant need for more sensitive collection methods and chemical analyses. In this study, we demonstrated the applicability of a surface enhanced Raman scattering (SERS) technique on the rapid and sensitive chemical analysis of individual nanoparticles. SERS technique provides a significant enhancement of the scattering efficiency over traditional Raman spectroscopy. The novelty of the proposed technique is that the SERS substrate is used directly as the sampling substrate of a condensational growth tube (CGT) sampler, which can activate nanoparticles into water droplets and ensure simultaneous inertial sampling and SERS pre-treatment. First, we investigated applicability of the method on mono-dispersed (20 nm, 50 nm, or 100 nm) ammonium sulfate (AS) and levoglucosan (LG) particles as model aerosols. The method was then applied to ambient nanoparticles. The successful detection of peaks corresponding to sulfate ν(SO42-) and organics ν(C-H) indicates that our proposed method to combine a CGT sampler and SERS showed a sensitivity high enough to provide deep insights into the chemical speciation of atmospheric nanoparticles as small as 20 nm in diameter.

To improve poor air quality in Asia and inform effective emission-reduction strategies, it is vital to understand the contributions of different pollution sources and their associated human health burdens. In this study, we use the WRF-Chem regional atmospheric model to explore the air quality and human health benefits of eliminating emissions from six different anthropogenic sectors (transport, industry, shipping, electricity generation, residential combustion, and open biomass burning) over South and East Asia in 2014. We evaluate WRF-Chem against measurements from air quality monitoring stations across the region and find the model captures the spatial distribution and magnitude of PM2.5 (particulate matter with an aerodynamic diameter of no greater than 2.5 µm). We find that eliminating emissions from residential energy use, industry, or open biomass burning yields the largest reductions in population-weighted PM2.5 concentrations across the region. The largest human health benefit is achieved by eliminating either residential or industrial emissions, averting 467 000 (95 % uncertainty interval (95UI): 409 000–542 000) or 283 000 (95UI: 226 000–358 000) annual premature mortalities, respectively, in India, China, and South-east Asia, with fire prevention averting 28 000 (95UI: 24 000–32 000) annual premature mortalities across the region. We compare our results to previous sector-specific emission studies. Across these studies, residential emissions are the dominant cause of particulate pollution in India, with a multi-model mean contribution of 42 % to population-weighted annual mean PM2.5. Residential and industrial emissions cause the dominant contributions in China, with multi-model mean contributions of 29 % for both sectors to population-weighted annual mean PM2.5. Future work should focus on identifying the most effective options within the residential, industrial, and open biomass-burning emission sectors to improve air quality across South and East Asia.

Heterogeneous oxidation of SO2 is one of the promising mechanisms to account for high loading of sulfate during severe haze periods in China. Our earlier work reported on the SO2 oxidation by OH and NO2 produced during 250 nm nitrate photolysis (Environ. Sci. Technol. Lett. 2019, 6, 86-91). Here, we extend that work to examine sulfate production during nitrate photolysis at 300 nm irradiation, which can additionally generate NO2- or HNO2, N(III). Flow cell/in situ Raman experiments showed that the reactive uptake coefficient of SO2, γSO2, can be expressed as γSO2 = 1.64 × pNO3-, where pNO3- is the nitrate photolysis rate in the range of (1.0-8.0) × 10-5 M s-1. Our kinetic model with the pNO3- predicts that N(III) is the main contributor to the SO2 oxidation, followed by NO2 contribution. Furthermore, the addition of OH scavengers (e.g., glyoxal or oxalic acid) does not suppress the sulfate production because of the reduced N(III)-consuming reactions and the high particle pH sustained by their presence. Our calculations illustrate that under characteristic haze conditions, the nitrate photolysis mechanism can produce sulfate at ∼1 μg m-3 h-1 at pH 4-6 and pNO3- = 10-5 M s-1. The present study highlights the importance of in-particle nitrate photolysis in heterogeneous oxidation of SO2 by reactive nitrogen (NO2-/HNO2 and NO2) under atmospherically relevant actinic irradiation. However, the nitrate photolysis rate constant needs to be better constrained for ambient aerosols.

Unexpectedly high amounts of aminium salts have been detected in ambient aerosol particles, prompting investigations into their role in new particle formation and nanoparticle growth. Amine uptake ...